Journal of South American Earth Sciences 108 (2021) 103183

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Journal of South American Earth Sciences

journal homepage: www.elsevier.com/locate/jsames

Genesis and classification of carbonate soils in the State of Rio de

Janeiro, Brazil
Carlos Roberto Pinheiro Junior a, Marcos Gervasio Pereira a, *, Antônio Carlos de Azevedo b,
Cornie Van Huyssteen c, Lúcia Helena Cunha dos Anjos a, Ademir Fontana d,
Eduardo Carvalho da Silva Neto a, Jonas Nunes Vieira a, Thairis Gomes Santos b
a
Universidade Federal Rural do Rio de Janeiro, Departamento de Solos, Seropédica, Rio de Janeiro, Brazil
b
Universidade de São Paulo, Escola Superior de Agricultura “Luiz de Queiroz”, Departamento de Ciência do Solo, Piracicaba, São Paulo, Brazil
c
Department of Soil, Crop and Climate Sciences at the University of the Free State, Bloemfontein Area, South Africa
d
Centro Nacional de Pesquisa de Solos – Embrapa Solos, Rio de Janeiro, Rio de Janeiro, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: Carbonate rocks occur in Brazil under diverse climatic and environmental conditions, and therefore are of great
Pedogenesis importance for pedological studies. The northwest region of the State of Rio de Janeiro, Brazil, is composed of
Amorphous carbonates calc-silicate rocks and marbles that occur under tropical climate with a long period of water deficit, which
WRB
provides conditions for peculiar pedogenesis. The objective of this study was to characterize the attributes of soils
Dolomitic
Kastanozems
formed from carbonate materials and to understand the role of the main factors and processes in pedogenesis, as
well as to provide information to the WRB (World Reference Base for Soil Resources) to improve carbonate soils
classification. A toposequence was selected in the municipality of Italva, RJ, Brazil, with six profiles being
described and sampled. All profiles presented median CaCO3 equivalent contents, high base saturation with the
predominance of Ca+2 and Mg+2, and high activity clay. The absence of effervescence and low CaO/MgO ratio
obtained by acid digestion suggest the dolomitic nature of the carbonates. Pedogenic carbonates were amor­
phous, since no XRD peaks were found. The high Mg+2 concentration provided by the parent material increases
the dispersion of clays and favors clay illuviation, which is manifested in the micromorphology through a large
amount of clay infillings and coatings. Four profiles on the highest part of the landscape were classified as
Kastanozems (Mollisols), the footslope profile as Fluvisol (Inceptisol), and the toeslope profile as Vertisol. The
mineralogy of the Vertisol’s clay fraction was predominantly composed of kaolinite interstratified with 2:1
phyllosilicates, mainly illite. Acid digestion can complete the analysis of the CaCO3 equivalent content by
quantifying CaO and MgO concentration in fine earth samples, presenting the potential to distinguish the
Dolomitic/Calcaric qualifiers. The recognition of Dolomitic/Calcaric qualifiers for the Kastanozem reference soil
groups is suggested, considering that the carbonate present in the calcic horizon may be diverse.

1. Introduction
Carbonate rocks occupy approximately 10% of the world’s land
surface and represent 20% of the sedimentary rocks of the Phanerozoic
eon (Ford and Williams, 2007) and therefore represent an important soil
parent material. Due to the wide extent of this lithology, studies that
seek to understand the influence of this material on pedogenesis and soil
characteristics are of great importance for pedological knowledge. The
role of inorganic carbon (soil and rock) in the global carbon cycle is also
vitally important, given the increased release of anthropic CO2 (Eswaran
et al., 1995; Gao et al., 2009). This further increases the urgency for
information on the fractionation of inorganic carbon amongst the
existing compartments and the mass transfer thereof between these.
Carbonate rocks are widely distributed in Brazil and thus occur
under widely different climatic and environmental conditions. Areas of
occurrence include the Jandaíra and Santana formations in Ceará state

* Corresponding author.
E-mail addresses: robertojrpinheiro@gmail.com (C.R. Pinheiro Junior), mgervasiopereira01@gmail.com (M.G. Pereira), aazevedo@usp.br (A.C. Azevedo),
vanHuyssteenCW@ufs.ac.za (C. Van Huyssteen), lanjosrural@gmail.com (L.H.C. Anjos), ademir.fontana@gmail.com (A. Fontana), netocseduardo@gmail.com
(E.C. Silva Neto), jonasnunesvieira@gmail.com (J.N. Vieira), thairis.santos@usp.br (T.G. Santos).

https://doi.org/10.1016/j.jsames.2021.103183
Received 22 November 2020; Received in revised form 14 January 2021; Accepted 15 January 2021
Available online 19 January 2021
0895-9811/© 2021 Elsevier Ltd. All rights reserved.
C.R. Pinheiro Junior et al.
(Northeast Brazil) (Brasil, 1981), the Una Group in Bahia state (North­
east Brazil) (Misi and Veizer, 1998), the Bambuí Group that occupies a
large part of the São Francisco Craton and extends through the states of
Goiás, Tocantins, Minas Gerais and Bahia (Central-West, North, South­
eastern and Northeast Brazil, respectively) (Santos et al., 2000; Reis,
2013; Ribeiro, 2016), the Bocaina Formation in Mato Grosso do Sul state
(Central-West Brazil) (Boggiani et al., 1993), and the Italva Group in Rio
de Janeiro state (Southeastern Brazil) (Brasil, 1983). All these carbonate
rocks are very complex, given the development of assemblages, at
different scales, and with differing dissolution and diagenesis, all of
which affect the carbonate rocks’ properties (Wennberg et al., 2016).
On a landscape scale, carbonate rock weathering and dissolution are
controlled by factors such as mineral composition, temperature, rainfall,
runoff, rock fracturing and vegetation (Kirstein et al., 2016). In soil
formation, topography and relief additionally control soil water dy­
namics such as drainage, erosion, and cation flow, and also influences
the solubilisation and reprecipitation of carbonates in the landscape.
Studying the genesis of soils in a carbonate toposequence, Pereira et al.
(2013) observed a reduction in calcium carbonate from the highest
parts, where drainage favoured carbonate solubilisation and leaching
and accumulation thereof in the lower parts of the landscape, where
precipitation was favoured. However, reprecipitation can also occur in
the highest parts of the landscape, where soils with a lithic contact in the
first few centimetres limit the leaching of Ca+2 (Maranhão et al., 2017).
The World Reference Base for Soil Resources (IUSS Working Group
WRB, 2015) defines dolomitic material as material that contains ≥2%
mineral material, with a CaCO3/MgCO3 ratio <1.5 and which strongly
effervesces with heated 1 M HCl, but only gives a weak retarded effer­
vescence with non-heated HCl. Dolomitic material is used as principal or
supplementary qualifier in the classification of 19 of the 32 Reference
Soil Groups.
The most used method for the quantification of carbonate in the soil
is solubilisation with HCl and the residue of the acid titrated with NaOH.
This methodology expresses the results in calcium carbonate equivalent
and does not differ from the ion (Ca2+, Mg2+ or Fe2+) associated with the
CO2−3 anion. However, the presence of Ca and/or Mg carbonates
Fig. 1. Location of study area in the municipality of Italva, Rio de Janeiro State, Southeastern Brazil.
2
Journal of South American Earth Sciences 108 (2021) 103183
produces important differences in the behaviour of clays and plants
(Kowalska et al., 2019). Carbonate soils are globally widespread
(Eswaran et al., 1995) and locally economically important (e.g. Fey,
2010). Several studies on the genesis and characterization of soils
formed from carbonate parent material (Alijani and Sarmadian, 2014;
Ferreira et al., 2016; Kowalska et al., 2019) have shown that these soils
typically have high concentration of calcium and magnesium, high base
saturation, high clay activity, and high calcium carbonate equivalent.
Despite this large body of knowledge, few studies quantify the CaO and
MgO content, necessary to evaluate the nature of carbonates present.
The objective of this study was therefore to characterize soils and to
elucidate the action of pedogenetic processes in a carbonate top­
osequence, with the aim of providing information to improve the clas­
sification of these soils in the World Reference Base for Soil Resources.
2. Material and methods
2.1. Location, physical environment, and sample collection
Six soil profiles located in the north western part of Rio de Janeiro
state in Brazil (Fig. 1) were studied. The region receives average annual
rainfall of 1092 mm, with a dry period from April to September, when
the average rainfall is less than 50 mm/month (Climate-Data.org, 2018).
The vegetation is tropical deciduous rainforest, with pronounced leaf
senescence in the dry period.
The study area occurs in the Italva geological Group, which is
composed of a metavolcano-sedimentary sequence, rich in marble and
calc-silicate rocks (Nogueira et al., 2012). The marble has varied
composition and may thus be calcitic or dolomitic. The calcitic marble
has coarse granulation, formed by calcite crystals of vitreous lustre,
while the dolomitic marble has a solid, microcrystalline, and milky
appearance (Tupinambá et al., 2007). Geomorphologically, the area is
characterized by interplanaltic depressions with mountain alignments,
characterized by alternating hills, low mountains, and mountains (Pin­
heiro Junior, 2018).
A toposequence (Fig. 2), consisting of six profiles, was selected for
C.R. Pinheiro Junior et al. Journal of South American Earth Sciences 108 (2021) 103183

Fig. 2. Soil profiles at summit position – P1; upper third backslope– P2; middle third backslope – P3; lower third backslope – P4; footslope – P5 and; toeslope – P6.

this study, searching a representative analyse of geomorphic surfaces of Santos et al. (2015). Disturbed samples for physical, mineralogical and
the landscape. Profiles were opened at the summit (P1), the upper third chemical analyses were collected from all horizons. These samples were
backslope (P2), the middle third backslope (P3), the lower third back­ air-dried, crushed, and sieved (<2 mm). Undisturbed samples, using
slope (P4), the footslope (P5), and the toeslope (P6) positions (Table 1). Kubiena boxes (Castro and Cooper, 2019) were collected for micro­
Morphological descriptions and effervescence tests with cold 10% morphological analyses.
HCl and with cold 10% H2O2 were done according to the methods of
2.2. Physical, chemical, mineralogical, and micromorphological analyses
Table 1
General landscape information and profile locations in the municipality of Coarse (2.0–0.2 mm) and fine sand (0.2–0.053 mm) fractions were
Italva, Rio de Janeiro State, Southeastern Brazil. quantified by sieving, while the total (dispersed) and natural (water
Prof. Coordinates Landscape Local Parent Drainage dispersed clay without use of dispersant) clay fraction were determined
position/ relief/ material using the pipet method (Day, 1965). Silt fraction was determined by
elevation declivity calculation (100 - coarse sand - fine sand - clay). Degree of flocculation
P1 21◦ 24′ 00.30′′ S Summit/ Plain/ Calc- Well (flocculated clay) was calculated as (total clay – natural clay) x
41◦ 39′ 40.90′′ E 86 m 3% silicate drained 100/total clay.
rocks Chemical analyses were performed using the methods of Teixeira
P2 21◦ 23′ 59.90′′ S Upper Wavy/ Calc- Well
et al. (2017). The attributes quantified were: a) pH in water and 1 mol
41◦ 39′ 41.90′′ E third/83 m 10% silicate drained
rocks and L− 1 KCl in 1:2.5 ratio; b) Ca, Mg, and Al contents by using 1 mol L− 1 KCl
marble extraction, with Ca and Mg being quantified by EDTA titration and Al by
P3 21◦ 23′ 58.70′′ S Middle Strong Colluvial Well NaOH titration; c) Na and K contents by using double acid extraction
41◦ 39′ 43.20′′ E third/72 m wavy/ sediments drained (HCl and H2SO4) and quantified by flame photometry; e) H + Al con­
25% of the Calc-
silicate
tents by using 0.5 mol L− 1 calcium acetate extraction and quantified by
rocks and titration with NaOH; and f) P values by the Olsen method (Olsen et al.,
marble 1954), using 0.5 mol L− 1 NaCO3, with pH adjusted to 8.5 and quantified
P4 21◦ 23′ 57.10′′ S Lower Wavy/ Colluvial Moderately by colorimetry. The ΔpH (pHKCl-pHH2O), sum of bases (S = Ca + Mg +
41◦ 39′ 45.00′′ E third/54 m 10% sediments drained
K + Na), effective cation exchange capacity of the soil (ECEC = Ca + Mg
of the Calc-
silicate + K + Na + Al + H), base saturation (BS = sum of bases/ECEC),
rocks and exchangeable sodium percentage (ESP = Na x 100/ECEC), and clay
marble activity (ECEC x 1000/Total clay contents) were calculated from the
P5 21◦ 23′ 56.80′′ S Footslope/ Plain/ Alluvial Imperfectly results.
41◦ 39′ 45.30′′ E 52 m 3% sediments drained
of the Calc-
To quantify the total organic carbon content, samples were ground
silicate by hand using a porcelain mortar and pestle to pass a 0.250 mm sieve. A
rocks and 0.167 mol L− 1 potassium dichromate solution (K2Cr2O7) in acid medium
marble was used as an oxidizing agent, and the excess was titrated with 0.20
P6 21◦ 23′ 55.20′′ S Toeslope/ Plain/ Colluvial Poorly
mol L− 1 ammonium ferrous sulphate solution with ferroin indicator
41◦ 39′ 48.00′′ E 46 m 2% and aluvial drained
sediments (Yeomans and Bremner, 1988).
of the Calc- For the extraction of SiO2, Fe2O3, Al2O3, and TiO2, the samples were
silicate solubilized in 1:1 H2SO4 solution, brought to boiling point and subse­
rocks and quently cooled and filtered. The iron, aluminium, and titanium con­
marble
centrations were determined, using UV–visible spectrophotometry of

3
C.R. Pinheiro Junior et al. Journal of South American Earth Sciences 108 (2021) 103183

the filtered solution, with silica being determined as the residue (Teix­ Table 2
eira et al., 2017). The following indices were calculated: Ki = Morphological attributes of the sampled soils in the municipality of Italva, Rio
(SiO2/Al2O3) x 1.7 and Kr = (SiO2/0.6)/((Al2O3/1.02)+(Fe2O3/1.60)). de Janeiro State, Southeastern Brazil.
Iron oxides were determined by extraction with a sodium dithionite- Hor Depth Munsell Colour Structure Textural
citrate-bicarbonate to quantify the total crystalline and low crystallinity (cm) class
forms (Fed) (Mehra and Jackson, 1960). Extraction with ammonium acid cm Matrix Mottled
oxalate quantified the low crystallinity forms (Feo) (McKeague and Day,
Profile 1 - Epileptic Calcic Kastanozem
1966). Iron concentrations in the extracts were determined by atomic Ak1 0–10 7.5 YR – mo, f and m, gr. Sandy clay
absorption spectrometry. Calcium carbonate equivalents were deter­ 2.5/3 loam
mined according with Teixeira et al. (2017). Ak2 10–22 7.5 YR – mo, f and m, gr. Sandy clay
To quantify the content of CaO and MgO, an acid digestion was 2.5/3 loam
ACk 22–29 7.5 YR – mo, f, gr. Sandy clay
performed according to USEPA (1996). The air-dried fine earth samples 2.5/3 loam
were taken to the block digester, where HNO3, H2O2, and HCl were Crk 29–40 7.5 YR – single grain Loam sand
added at different stages with subsequent filtering of the extract, from 4/3
which readings were taken in an atomic absorption device to quantify Profile 2 - Calcic Kastanozem (Cambic)
Ak 0–15 10 YR 3/ mo, vf and f, gr Sandy clay
the contents of Ca and Mg, which were later expressed as an oxide. –
3 loam
Minerals were identified by X-ray diffraction (Jackson, 1985). In brief, 5 ABk 15–32 10 YR 3/ – mo, vf and f, gr Sandy loam
g pf fine earth (soil passing a 2 mm sieve) was suspended into 200 ml 3
deionized water and sonicated for 3 min, passed through a 0.05 mm Bk 32–44 10 YR 3/ – we, f, abk and Sandy loam
sieve and the material retained was sonicated again for 4 min and sieved 3 sbk
Crk1 44–70 10 YR 3/ massive Sandy loam
again. Sand (retained onto the 0.05 mm sieve), silt and clay (further
–
4
separated into the centrifuge) were dried into a 40C oven. Soil fraction Crk2 70–107 +
10 YR 4/ – massive Loam sand
were irradiated, treated with HCl in excess (to destroy crystalline car­ 4
bonates) and the irradiated again. In addition, clay aliquots were treated Profile 3 - Luvic Calcic Kastanozem (Colluvic)
Ak 0–14 7.5 YR mo, f and m, gr Sandy clay
with DCB (deferrified clay fraction) and saturated with K and Mg (by –
3/3 loam
washing them 3 times with KCl or MgCl2 1 mol L− 1 solutions, and then 3 ABk 14–33 7.5 YR – mo, f, gr Sandy clay
times with 50% water diluted ethanol) and oriented mounted. Potas­ 3/3 loam
sium saturated clay slides were heated to 25 (K25), 300 (K300) and 550 BAtk 33–55 7.5 YR – st, f, pr cb mo, f, Sandy clay
(K550) Celsius degrees, and Mg (Mg25) slides were further saturated 3/4 abk
Btk1 55–82 5 YR 3/4 st, f, pr cb st, m, Sandy clay
with glycerol (Mg + G). All samples were Cu Kalpha (15 kV, 10 mA)
–
abk
irradiated in a Rigaku miniflex II system, equipped with graphite Btk2 82–103 5 YR 3/4 – st, m, pr cb st, m, Clay
monochromator, from 3 to 60 2theta degrees, 0.01 2theta degree step abk
per second. Btk3 103–144 5 YR 4/4 st, m, pr cb mo, Clay
+
–
m, abk
Micromorphological characterization was done on undisturbed
Profile 4 - Luvic Calcic Kastanozem (Colluvic)
samples from the Kubiena boxes, which were dried, impregnated with Ak1 0–9 7.5 YR – mo, f and m, gr Sandy loam
polyester resin, cut, and ground to prepare thin slides. The slides were 2.5/2
subsequently observed under a petrographic microscope and the Ak2 9–28 7.5 YR – mo, f and m, gr Sandy clay
micropedological description performed (Stoops, 2003). 3/3 loam
Ak3 28–43 7.5 YR – mo, f, gr Sandy clay
4/2 loam
2.3. Soil classification ABk 43–55 7.5 YR – mo, f, pr cb mo, f, Sandy clay
3/2 abk loam
Soils were classified according to the World Reference Base for Soil BAtk 55–74 7.5 YR – mo, m, pr cb mo, Sandy clay
3/1 f, abk loam
Resources (IUSS Working Group WRB, 2015) and Soil Taxonomy (Soil
Btk1 74–105 7.5 YR – st, m, pr Sandy clay
Survey Staff, 2014), based on the determined morphological, physical, 3/2 loam
chemical, and mineralogical attributes. Btk2 105–134 7.5 YR – st, co, pr Sandy clay
3/2 loam
3. Results Btk3 134–174+ 7.5 YR – st, co, pr Sandy clay
3/3
Profile 5 - Eutric Dolomitic Gleyic Fluvisol
3.1. Soil morphology Ak1 0–7 7.5 YR – we, f and m, gr Sandy clay
4/1 loam
Profile depth varied from 40 cm (P1) and 174 cm (P4) (Table 2). We Ak2 7–15 7.5 YR – mo, f and m, gr Sandy clay
3/2 loam
observed a predominance of dark colours, with low Munsell chroma
2Ak3 15–22 7.5 YR – we, m, gr Sandy clay
were observed in the surface horizons of all profiles, with a tendency to 3/2 loam
decreased darkening in the subsurface, except for P4, where there was a 3Bk1 22–40 7.5 YR – mo, m, abk and Sandy clay
strong darkening in the entire profile. Greyish colours were observed in 3/2 sbk
the subsurface of P5 and in all horizons of P6. Yellowish hues (7.5 YR 4Bk2 40–58 7.5 YR 5 YR 4/5 mo, m, pr cb mo, Sand clay
4/2 m, abk loam
and 10 YR) predominated in all profiles, with only P3 presenting an 5Ck 58–64 10 YR 3/ 5 YR 5/8 single grain Loam sand
orange hue (5 YR) in the subsurface horizons. 3
Secondary carbonate accumulation in the form nodules, approxi­ 6Cgk 64–97+ 7.5 YR 5 YR 5/8 massive Sandy clay
mately 2 cm in diameter and spherical in shape were observed in the Ak1 3/2
Profile 6 - Calcic Vertisol (Calcaric, Gilgaic, Gleyic)
horizon of P5 and in the Agk2, ABgk, and 3Bgk horizons of P6. Man­
Agk1 0–7 7.5 YR – st, f and m, gr Clay loam
ganese concretions, which were hard, purple internally and orange 4/1 and st, f, abk
externally, and soft, purple internally and externally were found in all Agk2 7–22 7.5 YR – st, f, gr and st, f, Clay
subsurface horizons of P6. 4/1 abk
The surface horizons were considered thick, ranging from 22 to 55 ABgk 22–34 – mo, m, abk

cm with a moderate granular structure predominating. In the subsurface (continued on next page)

4
C.R. Pinheiro Junior et al. Journal of South American Earth Sciences 108 (2021) 103183

Table 2 (continued ) The CaCO3 equivalents were high, with an average of approximately
Hor Depth Munsell Colour Structure Textural 170 g kg− 1 and a small variation with depth (Table 5). The highest
(cm) class variation was in P6, where it ranged from 98 to 234 g kg− 1. MgO and
cm Matrix Mottled
CaO values ranged from 0.3 to 10.5 g kg− 1 and from 0.1 to 10.5 g kg− 1,
respectively. The highest MgO values were in the profiles located at the
7.5 YR Sandy clay
summit and upper third backslope positions (P1 and P2) and highest
4/1 loam
2BAgk 34–47 7.5 YR – mo, m, abk and Sandy clay CaO values were found in P1 and P6. The CaO/MgO ratios ranged from
4/1 sbk loam 0.1 in P2 to 6.7 in P6. Effervescence reaction was absent on all horizons
3Bgk 47–90 10 YR 5/ 10 YR 5/ st, vc, pr Sandy clay of P1, P2, P3, and P4, while it varied from weak to moderate in the Ak1
1 8 horizon of P5 and almost all horizons of P6. In addition, for most hori­
3Cgk 90–105+ 10 YR 6/ 10 YR 5/ massive Sandy clay
1 6
zons with absent effervescence reaction, MgO values were higher than
CaO values (CaO/MgO < 1.0).
Legend: Hor.: horizon; we: weak; mo: moderate; st: strong; vf: very fine; f: fine; SiO2 was the main component of the clay fraction, with values
m: medium; co: coarse; vc: very coarse; gr: granular; ank: angular blocky; sbk:
ranging between 47 and 215 g kg− 1, especially for P5, where there was
subangular blocky; pr: prismatic; cb: composed by.
also an irregular distribution of these (Table 6). Fe2O3 and TiO2 values
were considered low, with maximum values of 67.0 and 9.0 g kg− 1
horizons of P3, P4, P5, and P6, the structure was strong prismatic. Gilgai respectively, in the Btk2 horizon of P3. The Ki index (SiO2/Al2O3) values
microrelief (Fig. 3a) and pressure surfaces (Fig. 3b) in the 3Bgk horizon were high, with an average of 3.0, reaching 4.95 on the Ak2 horizon of
of P6, was observed in the toeslope of the toposequence. P1, while the lowest values were observed in the subsurface horizons of
P3 with 2.20, 2.27, and 2.09 in Btk1, Btk2, and Btk3, respectively. The
3.2. Physical attributes Kr index (SiO2/Al2O3 + Fe2O3) values were all higher than 1.70. The
Al2O3/Fe2O3 ratios were 2.82 on average, with a minimum of 1.30.
In general, there was a predominance of the clay loam textural class The total free iron content (Fed) ranged from 3 to 28 g kg− 1, while the
in almost all horizons. The highest sand fractions were observed in the low crystallinity forms (Feo) ranged from 1 to 16 g kg− 1. The highest Fed
saprolite horizons (Crk) of P1 and P2 (Table 3). The coarse sand/fine was found in the subsurface horizons of P4, while the lowest content was
sand ratio ranged from 1.6 to 84.2 in P5 and from 1.6 to 5.2 in P6. found in the 5Ck1 horizon of P5. In general, the highest Feo/Fed ratios
The total clay content varied from 90 to 555 g kg− 1. There was an were observed in the surface horizons, which then decreased with depth,
increase in clay with depth, from 244 (ABk) to 555 g kg− 1 (Btk2) in P3 except for the lithological discontinuity profiles (P5 and P6) and for
and from 190 (Ak1) to 398 g kg− 1 (Btk1) in P5. In almost all horizons, some P3 horizons. The Feo/Fed ratio ranged from 0.08 to 0.52, with the
the degree of flocculation was below 50%. Only the Btk2 and Btk3 ho­ highest values in the lower parts of the landscape (P4, P5, and P6).
rizons of P3 did not have high activity clay (CEC ≥24 cmolc kg− 1 clay),
probably due to the lower values of the SiO2/Al2O3 ratio. 3.4. Sand, silt and clay mineralogy

3.3. Chemical attributes
The soil reaction classes ranged from moderately acid to alkaline,
with pH (H2O) ranging between 5.9 and 8.6, and all with negative ΔpH
values (Table 4). The base saturation varied from 82 to 100%, with Ca2+
and Mg2+ ions predominating on the adsorption complex. Na+ was
higher than K+ in all profiles. Al3+ concentrations were null, while P
contents were all lower than 9 mg kg− 1.
The highest total organic carbon contents (TOC), close to 20 g kg− 1,
were found in the surface horizons and decreased with depth in all
studied profiles, except for P5, where there was an irregular decrease.
In general, there was a predominance of quartz in all horizons.
Feldspars were also common, but less abundant than quartz. Amphi­
boles appeared in the sand fraction of P1, but not in the other profiles.
Mica was detected in the profiles located in the highest part of the
landscape (P1 and P2), but the reflections were wide at the base. The
presence of pyroxene was also verified in the horizons Btk2 of P3, Btk2
of P4, and 4Bk2 of P5.
Although no clear carbonate peaks were observed, rhodochrosite
(manganese carbonate) may be present on the Bk horizon of P2. In the
same horizon, there was a strong and well-defined peak at a very low
angle (48.9◦ 2theta, 0.18 nm) that may be vaterite, an intermediate form

Fig. 3. Gilgai microrelief (a) and compression surface (b) in the horizon 3Bgk of P6, in the toeslope. Photos: Marcos Gervasio Pereira.

5
C.R. Pinheiro Junior et al. Journal of South American Earth Sciences 108 (2021) 103183

Table 3
Physical attributes of the sampled soils in the municipality of Italva, Rio de Janeiro State, Southeastern Brazil.
Hor. Depth (cm) Sand Silt Clay Silt . Coarse sand Flocculated clay CEC clay
Clay Fine sand
Total Fine Coarse Total Nat.

————————————g kg− 1———————————— % cmolc kg− 1

Profile 1 - Epileptic Calcic Kastanozem

Ak1 0–10 514 203 311 212 274 96 0.8 1.5 65 –
Ak2 10–22 563 194 369 210 227 141 0.9 1.9 38 –
ACk 22–29 623 168 455 91 286 147 0.3 2.7 49 –
Crk 29–40 770 93 677 140 90 9 1.6 7.3 90 –
Profile 2 - Calcic Kastanozem (Cambic)
Ak 0–15 698 127 571 92 210 81 0.4 4.5 61 –
ABk 15–32 685 174 511 138 177 35 0.8 2.9 80 –
Bk 32–44 740 110 630 84 176 77 0.5 5.7 56 64.2
Crk1 44–70 682 87 595 174 144 59 1.2 6.8 59 63.5
Crk2 70–107+ 870 77 793 22 108 16 0.2 10.3 85 80.3
Profile 3 - Luvic Calcic Kastanozem (Colluvic)
Ak 0–14 616 149 467 94 290 150 0.3 3.1 48 –
ABk 14–33 630 154 476 126 244 130 0.5 3.1 47 –
BAtk 33–55 536 171 365 26 438 255 0.0 2.1 42 24.8
Btk1 55–82 416 130 286 92 492 328 0.2 2.2 33 25.6
Btk2 82–103 344 119 225 101 555 405 0.2 1.9 27 22.3
Btk3 103–144+ 351 112 239 111 538 376 0.2 2.1 30 20.0
Profile 4 - Luvic Calcic Kastanozem (Colluvic)
Ak1 0–9 639 175 464 171 190 54 0.9 2.7 72 –
Ak2 9–28 649 151 498 107 244 84 0.4 3.3 66 –
Ak3 28–43 618 151 467 130 252 92 0.5 3.1 63 –
ABk 43–55 621 133 488 114 265 181 0.4 3.7 32 –
BAtk 55–74 570 132 438 110 320 177 0.3 3.3 45 42.1
Btk1 74–105 503 128 375 154 343 271 0.4 2.9 21 37.4
Btk2 105–134 500 107 393 102 398 304 0.3 3.7 24 29.6
Btk3 134–174 +
523 96 427 88 389 313 0.2 4.4 20 27.0
Profile 5 - Eutric Dolomitic Gleyic Fluvisol
Ak1 0–7 545 208 337 165 290 156 0.6 1.6 46 –
Ak2 7–15 567 142 425 135 298 153 0.5 3.0 49 –
2Ak3 15–22 654 97 557 144 202 116 0.7 5.7 43 –
3Bk1 22–40 457 197 260 174 369 207 0.5 1.3 44 44.5
4Bk2 40–58 542 147 395 147 311 222 0.5 2.7 29 40.8
5Ck 58–64 852 10 842 85 63 36 1.3 84.2 43 –
6Cgk 64–97 +
515 95 420 133 352 235 0.4 4.4 33 32.5
Profile 6 - Calcic Vertisol (Calcaric, Gilgaic, Gleyic)
Agk1 0–7 432 167 265 201 367 223 0.5 1.6 39 –
Agk2 7–22 430 134 296 160 410 273 0.4 2.2 33 –
ABgk 22–34 560 172 388 94 346 224 0.3 2.3 35 –
2BAgk 34–47 655 106 549 141 204 183 0.7 5.2 10 56.5
3Bgk 47–90 494 103 391 82 424 349 0.2 3.8 18 35.5
3Cgk 90–105 +
488 110 378 22 490 355 0.0 3.3 28 33.3

Legend: Hor. = Horizon; Nat. = natural (undispersed) clay; Flocculated clay = (total clay – natural clay) x 100/total clay.

of calcium carbonate, between the amorphous calcium carbonates and
calcite, which also may be associated with biomineral processes (Bots
et al., 2012). However, further analysis is needed to test this hypothesis.
The silt fraction had generally the same minerals than the sand fraction,
but the quartz peaks were less pronounced (Fig. 5).
The XRD patterns observed in the clay fraction (Figs. 4–6) showed
the presence of illite and kaolinite in all horizons. The reflections of illite
were well expressed except in P6. In this sample, a small peak at 1.4 nm
and the assymetry in the kaolinite peak suggest the interstratification is
in more advanced stage and illitic layers are not present anymore. The
specific sample preparation and profile modelling needed to better
characterize the interstratified minerals could not be done, but the great
values of clay activity are in accord with the occurrence of such min­
erals. The kaolinite reflections disappeared after 500 ◦ C treatments, but
a small amount of chlorite should be present, at least in the 3Bgk horizon
of P6, where the 2:1 phyllosilicate peak appeared only after the elimi­
nation of kaolinite at 500 ◦ C.
3.5. Micromorphology
A moderate angular blocky type microstructure was verified in all
horizons, with some subangular blocky types occurring in the Btk2 of
P3, and the Btk2/Btk3 of P4. In all horizons the relative distribution was
porphyric. The predominant void types were chambers and planar in the
inter-aggregates, micro planar in the intra-aggregates, and channels and
holes in trans-aggregates.
The nature of coarse material in the studied horizons was similar,
with the predominance of quartz, feldspar, and mica with different de­
grees of alteration and grains with undulating surfaces. The degree of
sorting of components varied from poorly sorted to unsorted, with
particles of various sizes, there is no dominant one (Table 7). In all
profiles, the fine material was composed of clay minerals and iron ox­
ides. However, in the Btk2/Btk3 of P4, in addition to these components,
organic material was observed. A high frequency of b-fabric was
observed in the slides, mainly in 3Bgk of P6, with the predominance of
several striated types, besides speckled granite and in mosaic.
Clay coatings with moderately oriented iron oxides and textural
infillings, consisting of material of the same nature were observed in
Btk2 (P3) and Btk2/Btk3 (P4), but which were more expressed in the
latter (Fig. 7). Biological features of roots with a parallel-striated b-
fabric following the root orientation were also observed. Quasicoatings
of amorphous iron were found in the Btk2 and Btk3 (P4), while hypo­
coatings of amorphous iron and typical and geodic impregnated man­
ganese nodules were found in the 3Bgk (P6).

6
C.R. Pinheiro Junior et al. Journal of South American Earth Sciences 108 (2021) 103183

Table 4
Chemical attributes of the sampled soils in the municipality of Italva, Rio de Janeiro State, Southeastern Brazil.
Hor. Depth pH H2O pH KCl ΔpH Al Ca Mg Na K H + Al P S T V ESP TOC
− 1 − 1 1
cm ————————————cmolc kg ———————————— mg kg % g kg−

Profile 1 - Epileptic Calcic Kastanozem

Ak1 0–10 7.21 6.39 − 0.8 0.0 13.0 6.5 0.27 0.16 0.7 5 19.6 20.3 97 1.3 24
Ak2 10–22 6.92 5.55 − 1.4 0.0 13.0 4.8 0.20 0.12 0.8 5 18.1 18.9 96 1.1 17
ACk 22–29 7.17 5.32 − 1.9 0.0 12.0 3.3 0.13 0.09 0.8 3 15.2 16.0 95 0.8 6
Crk 29–40 7.33 5.55 − 1.8 0.0 6.9 2.2 0.09 0.06 0.5 3 9.2 9.7 95 0.9 4
Profile 2 - Calcic Kastanozem (Cambic)
Ak 0–15 6.27 4.74 − 1.5 0.0 8.0 4.3 0.18 0.11 2.0 5 12.6 14.6 86 1.2 14
ABk 15–32 6.52 4.56 − 2.0 0.0 7.4 2.6 0.10 0.07 1.3 4 10.2 11.5 89 0.9 8
Bk 32–44 6.71 4.43 − 2.3 0.0 7.0 3.1 0.12 0.08 1.0 6 10.3 11.3 91 1.1 6
Crk1 44–70 6.85 4.52 − 2.3 0.0 4.8 3.3 0.13 0.09 0.8 4 8.3 9.1 91 1.4 7
Crk2 70–107+ 6.98 4.85 − 2.1 0.0 2.2 5.3 0.22 0.14 0.8 5 7.9 8.7 90 2.5 1
Profile 3 - Luvic Calcic Kastanozem (Colluvic)
Ak 0–14 6.56 5.21 − 1.4 0.0 6.1 4.7 0.19 0.12 1.5 6 11.1 12.6 88 1.5 12
ABk 14–33 6.51 4.91 − 1.6 0.0 5.7 2.4 0.09 0.06 1.3 6 8.3 9.6 86 0.9 9
BAtk 33–55 6.83 5.13 − 1.7 0.0 6.3 3.2 0.13 0.08 1.2 7 9.7 10.9 89 1.2 6
Btk1 55–82 7.21 5.73 − 1.5 0.0 6.5 4.8 0.20 0.12 1.0 7 11.6 12.6 92 1.6 8
Btk2 82–103 7.23 5.8 − 1.4 0.0 6.1 5.1 0.21 0.13 0.8 6 11.5 12.4 93 1.7 7
Btk3 103–144+ 7.14 5.89 − 1.3 0.0 5.6 4.2 0.17 0.11 0.7 7 10.1 10.7 94 1.6 6
Profile 4 - Luvic Calcic Kastanozem (Colluvic)
Ak1 0–9 5.96 4.95 − 1 0.0 5.3 3.2 0.13 0.08 2.1 7 8.7 10.9 80 1.2 19
Ak2 9–28 6.10 4.63 − 1.5 0.0 5.8 2.2 0.09 0.06 1.7 4 8.1 9.8 83 0.9 9
Ak3 28–43 6.50 4.81 − 1.7 0.0 6.1 2.7 0.11 0.07 1.2 5 9.0 10.1 89 1.1 4
ABk 43–55 6.43 4.59 − 1.8 0.0 5.5 3.6 0.15 0.09 0.3 7 9.3 9.7 97 1.5 5
BAtk 55–74 6.43 4.18 − 2.3 0.0 5.3 5.2 0.21 0.13 2.6 7 10.8 13.5 80 1.6 8
Btk1 74–105 6.07 4.34 − 1.7 0.0 4.5 5.8 0.24 0.15 2.1 8 10.7 12.8 83 1.9 8
Btk2 105–134 5.85 4.29 − 1.6 0.0 4.3 5.0 0.20 0.13 2.1 7 9.6 11.8 82 1.7 8
Btk3 134–174+ 6.25 4.57 − 1.7 0.0 3.8 4.9 0.20 0.13 1.5 6 9.0 10.5 86 1.9 7
Profile 5 - Eutric Dolomitic Gleyic Fluvisol
Ak1 0–7 6.85 5.83 − 1.0 0.0 9.8 4.0 0.16 0.10 1.3 9 14.1 15.4 91 1.0 14
Ak2 7–15 7.17 6.02 − 1.2 0.0 10.0 3.7 0.15 0.10 0.5 7 13.9 14.4 97 1.0 14
2Ak3 15–22 7.34 6.13 − 1.2 0.0 7.2 3.0 0.12 0.08 0.7 6 10.4 11.1 94 1.1 9
3Bk1 22–40 7.10 5.87 − 1.2 0.0 11.0 4.4 0.18 0.11 0.8 8 15.6 16.4 95 1.1 15
4Bk2 40–58 7.34 5.76 − 1.6 0.0 7.8 3.8 0.15 0.10 0.8 8 11.9 12.7 93 1.2 7
5Ck 58–64 7.36 5.85 − 1.5 0.0 1.9 1.1 0.04 0.03 0.2 6 3.1 3.2 95 1.3 2
6Cgk 64–97 +
7.4 5.89 − 1.5 0.0 5.3 5.3 0.22 0.14 0.5 7 11.0 11.4 96 1.9 6
Profile 6 - Calcic Vertisol (Calcaric, Gilgaic, Gleyic)
Agk1 0–7 8.10 7.17 − 0.9 0.0 13.0 8.0 0.33 0.20 0.0 5 21.6 21.6 100 1.5 20
Agk2 7–22 8.47 7.35 − 1.1 0.0 10.0 6.9 0.28 0.17 0.0 6 17.6 17.6 100 1.6 10
ABgk 22–34 8.64 7.37 − 1.3 0.0 9.0 6.1 0.25 0.15 0.0 5 15.5 15.5 100 1.6 8
2BAgk 34–47 8.60 7.31 − 1.3 0.0 8.0 3.3 0.13 0.09 0.0 8 11.5 11.5 100 1.1 6
3Bgk 47–90 8.16 7.09 − 1.1 0.0 9.7 5.0 0.20 0.13 0.0 4 15.0 15.0 100 1.3 2
3Cgk 90–105 +
7.88 7.04 − 0.8 0.0 11.0 4.9 0.20 0.13 0.0 4 16.3 16.3 100 1.2 2

Legend: Hor. = horizon; S = sum of exchangeable bases; T = CEC at pH 7,0; V% = (S/T) x 100; ESP = exchangeable sodium percentage (100 Na+/T); TOC = total
organic carbon.

3.6. Soil classification qualifier is suggested, resulting in classification as Luvic Dolomitic

Regarding classification, P1 was classified as an Epileptic Calcic
Kastanozem according to the WRB (IUSS Working Group WRB, 2015),
and as Lithic Calciudolls according Soil Taxonomy, because it presented
a mollic superficial horizon, calcic horizon, high base saturation, and
lithic contact ≤50 cm from the surface. The lithic contact at P1 occurred
at 40 cm. In addition, P1 had a CaO/MgO ratio <1.5, suggesting the
inclusion of the Dolomitic qualifier, which would result in Epileptic
Dolomitic Kastanozem.
Profile P2 was classified as Calcic Kastanozem (Cambic) in the WRB,
and as Typic Calciudolls in the Soil Taxonomy, representing a mollic
horizon and a calcic horizon, coinciding with a cambic horizon. How­
ever, this profile also has a saprolitic horizon (Cr) ≤100 cm from the
surface and a CaO/MgO ratio <1.5. It is therefore suggested that the
qualifiers Saprolitic and Dolomitic should be included, which would
cause P2 to classify as Dolomitic Kastanozem (Cambic, Saprolitic).
Profiles P3 and P4 were both classified as Luvic Calcic Kastanozem
(Colluvic) in the WRB, and as Calcic Argiudolls in the Soil Taxonomy,
due to the presence of a mollic horizon, calcic horizon, clay accumula­
tion (B/A ratio >1,4) associated with high base saturation (>50%), high
clay activity (>24 cmolc kg− 1), and colluvial parent material. However,
the CaO/MgO ratio in both profiles is < 1.5, and thus the Dolomitic
Kastanozem (Colluvic).
Profile P5 was classified as Eutric Dolomitic Gleyic Fluvisol in the
WRB, and as Fluventic Eutrudepts in the Soil Taxonomy, because it had a
lithological discontinuity, CaO/MgO ratio <1.5 in most subsurface ho­
rizons, gleyic colour pattern, and high base saturation (>50%).
Lastly, profile P6 was classified as Calcic Vertisol (Calcaric, Gilgaic,
Gleyic) in the WRB, and as Typic Calciaquerts in the Soil Taxonomy, due
to the presence of a vertic horizon, calcic horizon, CaO/MgO ratio >1.5,
gleic properties, and gilgai microrelief. Although all the criteria of the
vertic horizon are not satisfied, this profile does present the typical
features attributed to the vertization process, such as compression sur­
faces and the occurrence of gilgai microrelief formed by the intense
expansion and contraction of the soil.
In general, there is strong correspondence between the classification
systems. The profiles classified as Kastanozems in the WRB (P1, P2, P3
and P4), were classified as Mollisols in Soil Taxonomy. The Fluvisol (P5)
was classified as Inceptisol in order level and as Fluventic in subgroup
level in the Soil Taxonomy, and P6 as Vertisol in both systems.

7
C.R. Pinheiro Junior et al. Journal of South American Earth Sciences 108 (2021) 103183

Table 5
CaCO3 equivalent, MgO and CaO contents and effervescence reaction with cold 10% HCl.
Horizon Depth CaCO3 eq. MgO CaO CaO/MgO Effervescence
− 1
cm ———————————————————g kg ——————————————————

Profile 1 - Epileptic Calcic Kastanozem

Ak1 0–10 187 10.5 10.5 1.0 Absent
Ak2 10–22 184 9.5 8.5 0.9 Absent
ACk 22–29 176 7.8 4.6 0.6 Absent
Crk 29–40 203 6.5 2.7 0.4 Absent
Profile 2 - Calcic Kastanozem (Cambic)
Ak 0–15 180 5.0 2.3 0.5 Absent
ABk 15–32 176 4.6 2.9 0.6 Absent
Bk 32–44 207 7.1 1.6 0.2 Absent
Crk1 44–70 172 7.9 1.2 0.2 Absent
Crk2 70–107+ 168 8.1 0.6 0.1 Absent
Profile 3 - Luvic Calcic Kastanozem (Colluvic)
Ak 0–14 180 1.9 1.0 0.5 Absent
ABk 14–33 141 1.5 1.1 0.7 Absent
BAtk 33–55 187 1.5 0.8 0.5 Absent
Btk1 55–82 141 1.2 0.6 0.5 Absent
Btk2 82–103 195 0.8 0.8 0.9 Absent
Btk3 103–144+ 168 0.6 0.4 0.7 Absent
Profile 4 - Luvic Calcic Kastanozem (Colluvic)
Ak1 0–9 152 1.8 1.9 1.1 Absent
Ak2 9–28 148 1.7 1.6 1.0 Absent
Ak3 28–43 113 1.6 1.3 0.8 Absent
ABk 43–55 141 1.7 1.3 0.8 Absent
BAtk 55–74 148 2.0 0.9 0.4 Absent
Btk1 74–105 156 1.7 0.9 0.5 Absent
Btk2 105–134 152 1.4 0.5 0.3 Absent
Btk3 134–174+ 152 1.1 0.4 0.4 Absent
Profile 5 - Eutric Dolomitic Gleyic Fluvisol
Ak1 0–7 160 1.5 2.9 2.0 Moderate
Ak2 7–15 160 1.3 2.6 1.9 Absent
2Ak3 15–22 191 1.2 2.2 1.9 Absent
3Bk1 22–40 187 1.7 2.4 1.4 Absent
4Bk2 40–58 180 1.4 1.5 1.0 Absent
5Ck 58–64 172 0.7 1.7 2.4 Absent
6Cgk 64–97 +
195 1.3 0.9 0.7 Absent
Profile 6 - Calcic Vertisol (Calcaric, Gilgaic, Gleyic)
Agk1 0–7 234 2.0 13.3 6.7 Moderate
Agk2 7–22 215 1.7 10.9 6.6 Moderate
ABgk 22–34 168 1.5 5.2 3.6 Moderate
2BAgk 34–47 98 0.7 2.9 4.0 Absent
3Bgk 47–90 176 0.3 1.5 4.5 Moderate
3Cgk 90–105 +
160 0.4 1.8 4.8 Weak

Legend: eq. = equivalent.

4. Discussion
4.1. Morphological and physical attributes
Profile depth increased down slope for the crest and backslope pro­
files, from 40 cm at P1 to 174 cm at P4. The profiles on the toeslope and
footslope were again shallower, at 97 cm and 104 cm respectively. This
might point to erosion at the higher lying positions, and concurrent
accumulation at the lower lying positions. Probably, the toeslope and
footslope profiles are deeper and have buried horizons, however, the
drainage conditions (imperfectly and poorly drained) made the evalu­
ation impossible. The quartz parent material of P1 might also provide
greater resistance to weathering and consequently limit soil depth, due
to the occurrence of the calc-silicate rocks.
A lithological discontinuity (Novaes Filho et al., 2012) was identified
at 58–64 cm (5Ck1) in P5, due to the increase in the coarse sand:fine
sand ratio, from around 2 to 84. This might point to differentially
deposited sediment, also because the profile is in the depositional point
of the landscape.
The low degree of flocculation in all profiles might be due to the high
Mg2+ concentration, which naturally acts as a dispersing agent (Corrêa
et al., 2003). This will also facilitate clay translocation in P3 and P4,
indicated by the clay increase with depth. The presence of high activity
clays in all profiles is associated with the climate, which minimizes silica
removal, as well as the higher SiO2 supply by the parent material.
The dark colours of the surface horizons are probably due to the
addition and transformation of organic matter from the added plant
residues. The dominant dark colours, even with low TOC contents, and
also in the subsurface horizons of P4, can also be explained by the
possible formation of calcium humus, which gives a greater recalci­
trance to the organic matter, allowing the expression of these colours
(Duchaufour, 1982). The grayish colours in P5 and P6 are probably due
to limited drainage that favours iron reduction and leaching. Under
restricted drainage conditions, water table oscillation intensifies the iron
and manganese oxy-reduction processes, and consequently the redis­
tribution and segregation (Kämpf et al., 2009), which explains the
manganese concretions in P6. These concretions have hardened and
present orange externally, probably due to higher oxygen and organic
matter concentrations in these environments. The predominance of
yellowish hues was explained by the low levels of iron and higher pH of
the parent material, which favour goethite formation (Medeiros et al.,
2013). P3, the only profile with orange colours (5 YR hue), also had the
highest Fe2O3 levels. Goethite was identified in the clay fraction (XRD
not shown) and the Fe–Mg silicates (amphiboles and pyronens) were
potential sources of iron to goethite formation.

8
C.R. Pinheiro Junior et al. Journal of South American Earth Sciences 108 (2021) 103183

Table 6
Pedogenetic oxides, Ki and Kr, total iron (Fed), and amorhous iron (Feo) values and their ratios.
Hor. Depth SiO2 Al2O3 Fe2O3 TiO2 Ki Kr Al2O3/Fe2O3 Fed Feo Feo/Fed Fed/Fet
− 1 − 1
cm ———————————g kg ——————————— ——g kg ——

Profile 1 - Epileptic Calcic Kastanozem

Ak1 0–10 141 70 59 7.7 3.42 2.22 1.86 6 4 0.63 0.10
Ak2 10–22 134 46 55 7.4 4.95 2.81 1.31 7 3 0.49 0.13
ACk 22–29 123 44 53 6.9 4.75 2.68 1.30 8 3 0.39 0.14
Crk 29–40 106 52 36 4.8 3.47 2.4 2.27 5 2 0.31 0.14
Profile 2 - Calcic Kastanozem (Cambic)
Ak 0–15 110 52 45 5.5 3.60 2.31 1.81 5 3 0.60 0.10
ABk 15–32 107 54 40 5.7 3.37 2.29 2.12 4 2 0.55 0.11
Bk 32–44 126 68 54 7.5 3.15 2.09 1.98 5 2 0.41 0.09
Crk1 44–70 156 85 59 8.9 3.12 2.16 2.26 5 2 0.41 0.08
Crk2 70–107+ 145 78 59 8.8 3.16 2.13 2.08 5 1 0.27 0.09
Profile 3 - Luvic Calcic Kastanozem (Colluvic)
Ak 0–14 144 87 51 7.5 2.81 2.05 2.68 8 2 0.24 0.16
ABk 14–33 115 74 40 6.7 2.64 1.96 2.90 8 2 0.23 0.20
BAtk 33–55 146 98 51 7.5 2.53 1.90 3.02 9 2 0.27 0.17
Btk1 55–82 188 145 66 8.8 2.20 1.71 3.45 10 3 0.27 0.15
Btk2 82–103 215 161 67 8.9 2.27 1.79 3.77 9 3 0.34 0.14
Btk3 103–144+ 194 158 64 8.8 2.09 1.66 3.88 10 2 0.19 0.15
Profile 4 - Luvic Calcic Kastanozem (Colluvic)
Ak1 0–9 104 55 34 5.7 3.21 2.3 2.54 8 4 0.49 0.23
Ak2 9–28 106 53 39 7.2 3.40 2.31 2.13 7 4 0.59 0.19
Ak3 28–43 126 71 38 6.8 3.02 2.25 2.93 9 5 0.49 0.25
ABk 43–55 119 64 41 6.5 3.16 2.24 2.45 13 3 0.26 0.32
BAtk 55–74 128 68 43 6.4 3.20 2.28 2.48 17 5 0.27 0.40
Btk1 74–105 145 95 52 8.1 2.59 1.92 2.87 20 5 0.22 0.39
Btk2 105–134 153 107 55 8.2 2.43 1.83 3.05 23 4 0.17 0.42
Btk3 134–174+ 160 114 55 8.3 2.39 1.82 3.25 28 2 0.08 0.52
Profile 5 - Eutric Dolomitic Gleyic Fluvisol
Ak1 0–7 136 84 44 5.8 2.75 2.06 3.00 18 10 0.59 0.40
Ak2 7–15 126 82 43 5.9 2.61 1.96 2.99 17 11 0.62 0.41
2Ak3 15–22 96 54 34 4.7 3.02 2.15 2.49 13 9 0.74 0.37
3Bk1 22–40 158 102 52 7 2.63 1.99 3.08 20 16 0.80 0.39
4Bk2 40–58 136 83 46 6.7 2.79 2.06 2.83 18 12 0.67 0.39
5Ck 58–64 47 17 14 1.5 4.7 3.08 1.91 3 2 0.74 0.23
6Cgk 64–97 +
146 96 52 7.5 2.59 1.92 2.90 23 3 0.14 0.44
Profile 6 - Calcic Vertisol (Calcaric, Gilgaic, Gleyic)
Agk1 0–7 170 108 39 5.9 2.68 2.17 4.35 8 2 0.28 0.20
Agk2 7–22 168 111 43 5.9 2.57 2.06 4.05 7 2 0.32 0.16
ABgk 22–34 138 89 36 5.7 2.64 2.09 3.88 9 3 0.37 0.25
2BAgk 34–47 100 62 35 4.7 2.74 2.01 2.78 7 4 0.57 0.21
3Bgk 47–90 172 125 45 5.6 2.34 1.90 4.36 13 2 0.15 0.29
3Cgk 90–105 +
176 129 46 5.8 2.32 1.89 4.40 10 2 0.15 0.23

Legend: Hor. = horizon; Ki: (SiO2/Al2O3) x 1.7; Kr = (SiO2/0.6)/((Al2O3/1.02)+(Fe2O3/1.60)); Fet = Fe2O3.

Fig. 5. XRD patterns of the silt fraction of selected horizons (P1: Hz ACk; P2: Hz
Fig. 4. XRD patterns of the sand fraction of selected horizons (P1: Hz ACk; P2:
Bk; P3:Hz Btk2; P4: Hz Btk2; P5: HZ 4Bk2; P6: Hz 3Bgk).
Hz Bk; P3:Hz Btk2; P4: Hz Btk2; P5: HZ 4Bk2; P6: Hz 3Bgk).

9
C.R. Pinheiro Junior et al.
Fig. 6. XRD patterns of the clay fraction (Mg + Glicerol) of selected horizons
(P1: Hz ACk; P2: Hz Bk; P3:Hz Btk2; P4: Hz Btk2; P5: HZ 4Bk2; P6: Hz 3Bgk).
Insert: Constancy of the Illite peak at 1.0 nm despite the expansion and
contraction treatments.
Fig. 7. Textural coatings (a) and infillings (b) and root biological feature with parallel striated b-fabric (c) in the Btk2 (P3); textural infillings (d), textural coatings
fissured (e) and, textural coatings and quasicoatings iron amorphous (f) in the Btk1/Btk2 (P4); typic nodule moderately impregnated (Q: quartz) (g), hypo and
quasicoatings iron amorphous (h) and, interior detail geodic nodule strongly impregnated (V: void) (i) in the 3Bgk (P6). Crossed polarized light (XPL): (a); (b); (c);
(d); (e); (f). Plane polarized light (PPL): (g); (h); (i).
10
Journal of South American Earth Sciences 108 (2021) 103183
4.2. Chemical attributes, sulfuric attack, and crystallinity of the iron
oxides
High pH values were related to the nature of the parent material,
providing high concentrations of basic cations, such as Ca2+ and Mg2+,
and an associated dry climate, which minimized their leaching. The
most alkaline soil reaction was observed in P6 and was related to its
position in the landscape, which favours the accumulation of basic
cations. Negative ΔpH values indicate the predominance of cation ex­
change capacity and the influence of high activity clays on these values.
The high pH caused the precipitation of exchangeable Al3+, resulting in
the observed null values thereof. This, and the high Ca2+ concentrations
favoured the formation of calcium phosphate (apatite) through covalent
bonding, reducing the plant availability of P and thus explain the low
levels of this element (Fink et al., 2016).
High Mg2+ concentration were similarly related to the parent ma­
terial, since dolomite dominates the region (Tupinambá et al., 2007).
The high soil Mg2+ values resulted in a suboptimal Ca:Mg ratio for the
good development of most crops (Lima et al., 2018). The dominance of
Na+ over K+ may be associated with the presence of calcium-sodium
plagioclase in the parent material (Nogueira et al., 2012). The Na+
concentrations were, however, insufficient to cause soil sodification, in
all soil profiles, the maximum exchangeable sodium percentage (ESP)
value was 2.5%.
The slight variation in CaCO3 equivalent in the profiles on the
highest parts of the landscape, together with the absence of carbonate
C.R. Pinheiro Junior et al.
Table 7
Micromorphological description of selected horizons from soils profiles from Italva, RJ, Brazil.
Horizon Degree of Relative b-fabric
sorting distribuition
Profile 3 - Luvic Calcic Kastanozem (Colluvic)
Btk2 Poorly Porphyric Stipple speckled e
sorted granostriated
Profile 4 - Luvic Calcic Kastanozem (Colluvic)
Btk2/ Poorly Porphyric Stipple speckled, porostriated,
Btk3 sorted granostriated
Profile 6 - Calcic Vertisol (Calcaric, Gilgaic, Gleyic)
3Bgk Unsorted Porphyric Mosaic-speckled, porostriated,
granostriated, stipple
speckled, randomly-striated.
nodules and the occurrence associated with the sand fraction, suggest a
geogenic nature or at most a small pedogenic influence, since calcium
solubilisation and subsequent precipitation would result in finer and
higher concentrations in the underlying horizons. P6 was the only pro­
file that presented a typical CaCO3 morphology of pedogenic origin, i.e.
calcium carbonate accumulation and precipitation, variation in CaCO3
content between horizons, and the presence of carbonate nodules
(Zamanian et al., 2016). Landscape dynamics and carbonate forms
appear to be strongly influenced by the climate of the study area. Despite
the dry climate, evidenced by the deciduous vegetation, precipitation
was enough to leach the soluble cations from the highest profiles in the
landscape, to accumulate in P6 or be leached out of the landscape.
As for the total oxides obtained by the sulfuric solubilisation, the
highest variability in SiO2 content, observed in P5 is also reflected in the
irregular distribution in the granulometry. Fe2O3 and TiO2 contents
were low, but like those reported by Maranhão et al. (2017) and Silva
et al. (2017), when studying the pedogenesis in carbonate areas of the
Jandaíra Formation of the Bambuí Group and the Bocaina Formation,
respectively, in Brazil. The high Ki index values indicate a low weath­
ering environment with low silica removal from the soil. The highest
values occurred in P1, where the greater proximity to the underlying
rock, in addition to being the main source of SiO2, hinders the vertical
flow of water and the consequent removal of silica. The lower Ki values
in P3 may be associated with the deposition of pre-weathered sediments,
with a lower Ki index, which also explains the lower clay activity
compared to the other profiles. Moreover, the Kr index indicates a small
contribution of iron and aluminium oxides in the chemical composition
of the fine earth fraction, similar to the Al2O3/Fe2O3 ratio indicating the
predominance of aluminium over iron.
The presence of minerals other than carbonate rocks not only mod­
ifies the effects of weathering on minerals (Hardt, 2004), but is also
responsible for the variability in the chemical composition of soils
formed. Although most of the studied soils have high Ki index values,
Silva et al. (2017) in a study of the genesis of soils formed from lime­
stones of the Bocaina Formation, observed profiles with Ki values lower
than 1.0, low levels of SiO2, Al2O3, Fe2O3, and TiO2, with CaCO3
equivalents higher than 700 g kg− 1, which was associated with a higher
purity of the limestone parent material.
Regarding the crystallinity of iron oxides, the Fed values were
considered low, which were close to those observed in several studies
conducted in the carbonate areas of Brazil (Ferreira, 2012; Silva, 2013;
Maranhão et al., 2017). The low iron content in the source material,
associated with the dry climate, minimizes weathering and consequent
release of iron (Kämpf and Curi, 2000). The high Feo/Fed ratio observed
in the surface horizons of almost all profiles was due to the complexation
of iron released from the primary minerals by organic matter, favouring
low crystallinity (Kämpf and Curi, 2000). Low Fed/Fes values indicate a
Journal of South American Earth Sciences 108 (2021) 103183
Microstructure/Pedality Pores Pedological features
Angular and subangular Intraggregates: micro Coatings and dense infillings (clay and iron
blocks/Moderately planar. oxides); root biological feature with parallel
developed Interaggregates: striated b-fabric.
chambers and planar.
Angular and subangular Intraggregates: micro Coatings and dense infillings (clay and iron
blocks/Moderately planar. oxides); quasicoatings (amorphous iron);
developed Interaggregates: root biological feature with parallel striated
chambers and planar. b-fabric.
Angular blocks/ Intraggregates: micro Hypocoatings (amorphous iron); typical and
Moderately developed planar. geodic impregnated manganeses nodules.
Interaggregates:
chambers and planar.
higher proportion of crystalline iron. The predominance of illite in the
clay fraction, with iron in its structure, confirms these results. The
highest values of these ratios were observed in the lower parts of the
landscape (P4, P5, and P6), which were associated with pre-weathering
of material before deposition, accelerating the weathering and conse­
quent release and precipitation of iron oxides.
4.3. Mineralogy
No crystalline forms of carbonates were identified. The carbonate
dynamics in the area should be strongly dictated by the rain regime.
Areas with annual precipitation greater than 1000 mm rarely have more
than 4 g kg− 1 C in the top 1 m soil (Zamanian et al., 2016). Therefore, in
Italva, lithogenic carbonates should dissolve in the wetter months
(October to March) and precipitate during the drier ones (less than 50
mm month− 1, April to September). During the drier period, amorphous
pedogenic carbonates should precipitate quickly. Amorphous phases are
usually highly reactive and therefore should be dissolved during the next
wet season. The XRD patterns of HCl treated and HCl untreated samples
did not differed (not shown). This would be in accord with the lack of
effervescence in P1 to P4. In addition, the abundance of Mg2+ activity
increases the amorphous carbonate stabilization and consequently hin­
ders the crystallization of calcite (Rodriguez-Blanco et al., 2012; Zhang
et al., 2017). On the contrary, amorphous carbonates with high Mg:Ca
ratios, as those observed in this study, acts as a precursor to proto­
dolomite (Rodriguez-Blanco et al., 2015)
According to Boggs (2009), kinetic factors prevent the formation of
stoichiometric or “ideal” dolomite. Among these, the rapid crystalliza­
tion of supersaturated solutions, which makes the organization of Ca2+
and Mg2+ in their appropriate layers difficult; the high energy required
for the dehydration of Mg2+, which favours the formation of phases
containing more calcium; and the low activity of CO−3 2, which inhibits
the precipitation of carbonates with high Mg2+ concentration and is also
associated with the high dehydration energy of this element. The
occurrence of vaterite in P1, if confirmed, would be in accordance with
this model in which crystalline carbonate crystals are difficult to form
and grow due to the pedo environmental conditions, as well as the high
Mg:Ca ratio of the parent material.
The mineralogy of the samples was more varied in the sand and silt
fractions than in the clay fraction (Figs. 4–6). In the sand fraction, quartz
and feldspar were present in all samples/profiles. Mica was found only
in P1 and P2 and amphibole only in P1. Mica and amphibole were
probably related to the parent material underneath P1 (see Fig. 1). The
sand fraction of the P2 to P6 profile had pyroxen in addition to quartz
and feldspar. P2 had also mica, possibly transported from P1 by short
distance erosion or colluviation, and P4 had a very small amount of
amphibole. Weathering of amphiboles and pyroxens were sources of Fe
11
C.R. Pinheiro Junior et al.
to iron oxides precipitation.
The greater occurrence of quartz in the sand fraction is due to the
calc-silicate nature of the parent material since this mineral is the main
impurity in the marbles of the region (Nogueira et al., 2012). Quartz rich
sand fraction was reported in other studies on pedogenesis in carbonate
rich environments (Pereira et al., 2013; Ferreira et al., 2016; Maranhão
et al., 2017). The silt fraction had quartz and feldspar in all samples. In
P1 mica and amphibole, and in P2, mica were present in silt as well as in
sand fractions. However, mica appeared in the silt fraction of P5,
together with a 1.4 mineral, possibly chlorite, and amphibole in the P5
and P6, kaolinite peaks of variable intensity appeared in all silt samples.
The identification of easily weatherable minerals in the sand and silt
fractions imply the weathering rates being slow or that fresh parent
material has been recently added to the profiles.
In the clay fraction diffractograms, all peaks in angles smaller than
15 2theta (Cu Kalpha), which is the range of the 1st order peaks of
phyllosilicates, had asymmetries that indicates the presence of in­
terstratifications, which would explain the high activity of the clay
fraction in all profiles except in the P3 (but even in this one, still close to
the limit). The kaolinite peaks of the 3Bgk horizon of P6 had a great full
width at half maximum (FWHM), suggesting small crystallite size, which
may favour the formation of the observed soil pores and vertic features.
Kaolinite had the strongest peaks in the clay fraction, followed by
illite. It seemed that illite was more abundant in the upper profiles (P1
and P2) than in the lower ones, which is related to the presence of micas
in their coarser fractions. A more detailed study of clay mineralogy of
these profiles should better express the interstratified nature of these
two phyllosilicates. Interestingly, P6 had vertic features and was the
profile with less pronounced 2:1 phyllosilicates peaks. Vertic properties
may develop in soils with small amount or absence of expandable
phyllosilicates (e.g. Heidari et al., 2004; Heidari et al., 2008; Maranhão
et al., 2020). Such phenomenon is not well understood but is being
attributed to two non excludent mechanisms. The first one is related to
the volume change caused by the presence of ultramicropores that
would impart capillary forces to the soil mass strong enough to move the
soil mass (Anderson et al., 1973; Wilding and Tessier, 1988; Olson,
2000; Schaetzl and Anderson, 2005). The second one is related to the
presence of highly active minerals in the fine clay (smaller than 0.2 μm),
non or hardly detected by routine X ray diffraction procedures. These
minerals would be haloisite (Malik, 1990), palygorskite and inter­
stratified minerals (varying among kaolinite, illite, and chlorite) (Yer­
ima et al., 1985, 1987; Schaetzl and Anderson, 2005; Heidari et al.,
2004). Of particular interest are the results reported by Heidari et al.
(2004), in which a very similar parent material as Italva, but under
different climate, they found vertic morphology in a soil which lack
smectitic minerals, but have palygorskite, illite, chlorite, and kaolinite
minerals in the fine clay fraction. A mineralogical assemblage similar to
the P6 profile, except possibly for the palygorklite. In addition, the
occurrence of the gilgai microrelief and pressure surfaces in the sub­
surface horizons of P6 are indicative of the intense movement of soil
material, typically associated with inversion, which may be associated
with humidity and drainage conditions that predispose the soil to
expansion and contraction (Kabala et al., 2015).
4.4. Micromorphology and soil genesis
Micromorphological evaluation of the coarse material with degree of
sorting poorly sorted and, undulating and irregular surface indicate a
low reworking of the sand grains during transport, which is associated
with high transport energy and rapid accumulation and suggested
gravitational colluvium as the dominant processes in the transport and
sedimentation of the parent material (Mücher et al., 2010).
Despite the low TOC content of the P4 subsurface, the Btk2/Btk3
slide showed dark colours due to the presence of organic matter in the
fine material, indicating melanisation (Fanning and Fanning, 1989).
This process may be associated with the formation of higher calcium
12
Journal of South American Earth Sciences 108 (2021) 103183
concentration humus, giving more recalcitrance to the organic matter
and allowing the expression of these colours (Duchaufour, 1982). This
process also seems to be acting on the superficial horizons of P1, P2, P3,
and P4, considering that they have average TOC content but very dark
colours, with value and chroma usually of 3/3.
Although all profiles have CaCO3 equivalents, the action of the
pedogenetic carbonation seems to be more evident in P5 and P6, since
these were the only ones with nodules, typically associated with pedo­
genic carbonates (Zamanian et al., 2016). However, these nodules were
observed only in the macromorphological observations.
Despite the dry climate conditions, the parent material provides high
concentration of Mg2+, dispersing the clays and favouring their mobi­
lization despite the small volume of water provided by the climate,
acting on the transport of particles. The action of this clay translocation
process (eluviation and illuviation) can be confirmed from the micro­
morphological analysis of the P3 and P4 subsurface horizons. The main
pedological features observed in the Btk2 (P3) and Btk2/Btk3 (P4) slides
were textural fillings and coatings (Holliday and Rawling, 2006). In
addition, the moderate drainage conditions in P4 could be evidenced by
amorphous iron oxide quasicoatings, indicating lower oxygen avail­
ability and redox processes at some time of the year (Lindbo et al.,
2010).
The large amount of b-fabric and planar porosity, especially in P6,
associated with the presence of compression surfaces and gilgai micro­
relief, were associated with vertization, since these are typical features
resulting from the intense expansion and contraction of clays (Kovda
and Mermut, 2010). This profile presented grayish colours and hypo­
coatings of amorphous iron and manganese nodules, formed in poorly
drained environments where redox reactions and gleization predomi­
nate (Lindbo et al., 2010).
4.5. Dolomitic and Calcaric qualifiers
Regarding classification, although the Dolomitic/Calcaric qualifier is
present in many reference groups in the WRB (IUSS Working Group
WRB, 2015), it is not used in the Chernozems, Kastanozems, and Cal­
cisols groups, which have calcic or petrocalcic horizons (CaCO3 equiv­
alent ≥15%). Therefore, the level of detail in the classification of these
groups is minimized, especially when formed from a parent material
with higher MgCO3 concentration. In this study, the most soil horizons
with CaO/MgO ratio less than 1.0 did not react to effervescence with
non-heated HCl, which shows the dolomitic nature of carbonates (Morse
and Mackenzie, 1990). In the WRB, Dolomitic and Calcaric qualifiers are
considered diagnostic material and the 1.5 value of the CaCO3/MgCO3
ratio divides them. However, considering the differences in the disso­
lution characteristics of carbonates (calcite, dolomite, magnesite, etc.)
(Chou et al., 1989; Pokrovsky et al., 2005), different chemical behav­
iours can be observed according to the pedoenvironment conditions.
Despite this, the presence of carbonates of different nature in the fine
fraction is strongly reflected in soil attributes and the expression of CaO
and MgO contents would help the interpretation of attributes such as the
Ca:Mg ratio and the high clay dispersion in soils with high exchangeable
Mg2+ concentration. In this sense, the use of simpler analyses such as the
acid digestion used by USEPA (1996), quantifying the CaO and MgO
concentration and the application of the CaO/MgO ratio to identify the
Dolomitic and Calcaric qualifiers are alternatives to better classify
carbonate-rich soils.
5. Conclusions
Tropical climate conditions with low rainfall season prevent the
precipitation of pedogenic carbonate minerals at higher points in the
landscape due to the good drainage conditions. On the contrary, the
formation of pedogenic carbonate minerals is facilitated by the topo­
graphical relief, resulting in the accumulation, fast precipitation, and
irregular distribution of carbonate minerals in lower landscape positions
C.R. Pinheiro Junior et al.
during the dry season.
Parent material providing high magnesium concentrations promotes
the dispersion of clays and favours clay eluviation and illuviation. The
vertization process, formation of compression surfaces, and gilgai
microrelief can occur in non-smectitic soils, but was reported before in
soils with interstratified kaolinite-2:1 minerals, suchas the illite found in
the present study.
In this study, acid digestion resulted in the complete analysis of
CaCO3 equivalent by quantifying CaO and MgO concentration in fine
earth samples, presenting the potential to define the Dolomitic and
Calcaric qualifiers. We therefore suggest the inclusion of these qualifiers
for the Kastanozem reference soil groups, since carbonate minerals in
calcic horizons may be diverse in nature and significantly impact on the
land use.
Author statement
Carlos Roberto Pinheiro Junior: Methodology, Formal analysis,
Investigation, Resources, Writing – original draft, Writing – review &
editing. Marcos Gervasio Pereira: Conceptualization, Methodology,
Investigation, Resources, Writing – original draft, Writing – review &
editing, Supervision, Project administration, Funding acquisition.
Antônio Carlos de Azevedo: Conceptualization, Methodology, Formal
analysis, Investigation, Resources, Writing – original draft, Writing –
review & editing, Supervision, Project administration, Funding acqui­
sition. Cornie Van Huyssteen: Writing – original draft, Writing – review
& editing, Supervision. Lúcia Helena Cunha dos Anjos: Writing – original
draft, Writing – review & editing, Supervision. Ademir Fontana - Formal
analysis, Writing – original draft, Writing – review & editing. Eduardo
Carvalho da Silva Neto - Formal analysis, Writing – original draft,
Writing – review & editing. Jonas Nunes Vieira: Formal analysis, Writing
– original draft, Writing – review & editing. Thairis Gomes Santos:
Formal analysis, Writing – original draft, Writing – review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgment
This study was financed in part by the Coordenação de Aperfeiçoa­
mento de Pessoal de Nível Superior - Brasil (CAPES) - Finance Code 001.
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